TWI534216B - Water - based metal surface treatment agent - Google Patents

Description

Aqueous metal surface treatment agent

The present invention relates to an aqueous metal surface treatment composition, a metal surface treatment method using the aqueous metal surface treatment composition, and a surface treatment metal sheet using the surface treatment composition, the aqueous metal surface treatment composition containing no chromium The non-polluting water-based metal surface treatment composition can replace the conventional chromate treatment and phosphate treatment to obtain an excellent film such as workability, corrosion resistance, and adhesion of the upper coating film, and is excellent in storage stability.

Conventionally, in order to improve the corrosion resistance of a metal surface, chromate treatment and phosphate treatment are generally performed. However, in recent years, the toxicity of chromium has become a social problem. The surface treatment method using chromate includes a problem of scattering of chromate soot in the treatment step, a large cost in the wastewater treatment facility, and a problem caused by dissolution of the chromic acid from the passivation treatment film.

Further, in the case of phosphate treatment, surface treatments of zinc phosphates and iron phosphates are usually carried out, but for the purpose of imparting corrosion resistance, after the phosphate treatment, chromic acid is usually used for the cleaning treatment, and thus chromium treatment is present. Problems, and in order to perform etching of a metal surface, there are wastewater treatment such as a reaction accelerator and/or metal ions such as a fluorine compound incorporated in a phosphate treatment agent, and from metal ions. Problems such as sludge treatment caused by elution of the treated metal.

As a treatment method other than the chromate treatment and/or the zinc phosphate treatment, the following methods and the like are proposed:

(1) A surface treatment method which is treated with an aqueous solution containing aluminum dihydrogen phosphate and then heated at a temperature of 150 to 550 ° C (see, for example, Patent Document 1).

(2) A method of treating with an aqueous solution containing tannic acid (for example, refer to Patent Document 2 or the like).

However, in the method of (1), when the coating material is applied thereon, the adhesion of the coating material is insufficient, and in the method (2), there is a problem that the corrosion resistance is poor.

In addition, as a zinc-based plated steel sheet having a film-like surface-treated coating film having a film thickness of several μm or less, for example, a rust-preventing steel sheet for cationic electrodeposition coating is known which passes zinc. The plated steel sheet is a base material, and a chromate coating film is formed thereon, and an organic composite tantalate coating film is further formed thereon as an uppermost layer, and the rust-preventing steel sheet for cationic electrodeposition coating has workability and Excellent performance in corrosion resistance. However, since the rust-preventing steel sheet has a chromate coating film, there is a problem of safety and hygiene caused by chromate ions as described above. Moreover, the corrosion resistance of the steel plate obtained by removing the chromate coating film from the rust preventive steel sheet is greatly lowered.

Patent Document 4 discloses a surface-treated steel sheet by using a surface treatment liquid containing a cationic polyurethane resin, a specific phenol resin, a decane coupling agent, a titanium compound, and a specific acid or a salt thereof. Surface of zinc-coated steel or aluminum-plated steel Obtained by processing. However, the balance of properties such as the flat portion corrosion resistance of the surface-treated steel sheet, the corrosion resistance of the processed portion, the fingerprint resistance, the coating adhesion, the workability, and the water resistance are not necessarily good.

Patent Document 5 discloses a single-coated aqueous coating material which uses an aqueous coating material for a steel sheet obtained by blending cerium oxide particles and an organic titanate compound in an aqueous dispersion resin to impart corrosion resistance, Solvent resistance, alkali resistance, coating adhesion, film adhesion, and bath stability are excellent.

In addition, a non-chromium surface is disclosed in Patent Document 6. The steel sheet is treated by using a cationic polyurethane resin having a specific resin compound (A) in a predetermined amount and having a cationic functional group selected from a primary amino group to a tertiary amine group and a quaternary ammonium salt group (B) The surface treatment agent of the decane coupling agent (C) and the specific oxygen compound (E) having a specific reactive group is excellent in corrosion resistance, and is excellent in fingerprint resistance, blackening resistance, and coating adhesion.

However, the technique described in Patent Document 5 or 6 stores In the case where the resin is an anion, the surface treatment film is weak in alkali resistance, and if it is cationic, the surface treatment film is weak in acid resistance, and its use is limited.

The following technique is disclosed in Patent Document 7: A treatment liquid obtained by containing an organic resin, a decane coupling agent, or a solid lubricant in an aqueous lithium niobate solution treats the surface of the metal plate. However, since the inorganic component is likely to form a hard polymer, the corrosion resistance of the processed portion such as the bending process is insufficient. In addition, since a large amount of alkali metal is contained, when an upper coating film is formed on the surface-treated steel sheet, the upper coating layer is applied. The secondary adhesion of the coating film is inferior.

As described above, it is impossible to obtain a surface treatment agent which can replace the chromate film by any of the methods. It is an urgent need to develop a surface treatment agent and a surface treatment method which can replace the chromate film.

[Patent Document 1] Japanese Patent Publication No. Sho 53-28857

[Patent Document 2] Japanese Laid-Open Patent Publication No. 51-71233

[Patent Document 3] Japanese Patent Laid-Open Publication No. 60-50180

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2003-105562

[Patent Document 5] Japanese Laid-Open Patent Publication No. 2001-353750

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2003-105562

[Patent Document 7] Japanese Patent Laid-Open No. Hei 11-58599

An object of the present invention is to provide an aqueous metal surface treatment composition, a metal surface treatment method using the surface treatment composition, and a surface treatment metal sheet obtained by surface treatment using the surface treatment composition, the aqueous metal surface treatment The composition does not contain a chromium compound, and can solve the problems in the prior art, has excellent storage stability, and can form corrosion resistance, mold processability, excellent coating adhesion, and acid resistance and alkali resistance on the surface of the metal material. Surface treatment of the film.

The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, found the following facts, so that the above object can be achieved and completed. The present invention is formed by blending a hydrolyzed co-condensate of an epoxy group-containing decane coupling agent with an alkoxy decane (condensate) and a colloidal cerium oxide in a predetermined amount in a specific aqueous organic resin. The water-based metal surface treatment composition is excellent in storage stability of the surface treatment composition, and the film formed of the surface treatment composition is extremely excellent in various properties such as corrosion resistance and moldability.

Thus, the present invention provides an aqueous metal surface treatment agent characterized in that it contains (A) a group consisting of a polyurethane resin, an epoxy resin, an acrylic resin, and a polyolefin resin according to a solid content. 100 parts by mass of at least one aqueous organic resin selected from the group; and 100 parts by mass of the resin solid content of the aqueous organic resin (A), containing (B) an epoxy group-containing decane coupling agent (a) Hydrolyzed condensate of the condensate (b) of at least one alkoxydecane compound and/or the alkoxydecane compound represented by the following formula [1], 0.1 to 40 parts by mass, (R) _4-n- Si -(X) _n [1]

(wherein R represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted by a substituent having no reactivity, X represents an alkoxy group, n represents an integer of 1 to 3), and (C) colloidal ceria 5.0 ~50 parts by mass.

Further, the present invention provides a metal surface treatment method characterized in that the aqueous metal surface treatment composition is applied to a metal coated article and dried.

Further, the present invention provides a surface-treated metal sheet by using the above-described aqueous metal surface treatment composition for a metal coated article The surface is treated with a surface.

The aqueous metal surface treatment composition of the present invention is a surface treatment composition containing no chromium compound, and can form a flat portion and/or a processed portion of the surface of the metal material, such as corrosion resistance, deep drawing processability, and the like. It is excellent in coating properties, and has a surface treatment film excellent in acid resistance, alkali resistance, and balance of properties, and is a composition excellent in storage stability.

The surface-treated metal sheet of the present invention is a surface-treated metal sheet obtained by surface-treating the surface of a metal object to be coated with the above-described aqueous metal surface treatment composition, and is a surface-treated metal sheet having excellent balance of various properties described above. The surface-treated metal sheet of the present invention can be used without applying a top coat or can be used by applying a top coat.

Further, the aqueous metal surface treatment composition of the present invention and the surface-treated metal sheet obtained by surface treatment using the treatment composition do not contain a chromium compound, thereby overcoming environmental problems.

[Best Mode for Carrying Out the Invention]

The aqueous metal surface treatment composition of the present invention contains (A) an aqueous organic resin, (B) a hydrolysis condensate of a condensate of an epoxy group-containing decane coupling agent and an alkoxy decane compound or the alkoxy decane compound, and (C) Colloidal cerium oxide as an essential component.

The components in the metal surface treatment composition of the present invention are described below.

Waterborne Organic Resin (A)

The aqueous organic resin as the component (A) of the metal surface treatment composition of the present invention is preferably at least one selected from the group consisting of a polyurethane resin, an epoxy resin, an acrylic resin, and a polyolefin resin. The organic resin, preferably an aqueous organic resin dissolved or dispersed in water, is usually supplied in the form of an aqueous solution or an aqueous dispersion.

Examples of the polyurethane resin include a polycondensate of a polyether polyol, a polyester polyol, a polycarbonate polyol, and the like, and a polycondensate of an aliphatic, alicyclic or aromatic polyisocyanate.

As a method of stably dispersing or dissolving the polyurethane resin in water, for example, the following method can be used. (1) a method of imparting hydrophilicity and dispersing or dissolving in water by self-emulsification by introducing an ionic group such as a hydroxyl group, an amine group or a carboxyl group to a side chain or a terminal of a polyurethane polymer; 2) a polymer obtained by using a emulsifier and a mechanical shearing force or a terminal isocyanate group by blocking with a blocking agent such as hydrazine, an alcohol, a phenol, a thiol, an amine or a sodium hydrogen sulfite. a method of forcibly dispersing a polymer in water; (3) mixing a urethane prepolymer having a terminal isocyanate group with water, an emulsifier, and an extender, and simultaneously performing dispersing using mechanical shearing force And a method of polymerizing; (4) using a water-soluble polyol such as polyethylene glycol as a polyol as a main raw material of the polyurethane to form a water-soluble polyurethane to be dispersed or dissolved in The method in the water, etc. Further, the molecular weight of the polyurethane resin is not particularly limited. By weight The average molecular weight is preferably from 10,000 to 1,000,000, preferably from 50,000 to 500,000.

Examples of commercially available products of the polyurethane resin include Hydran HW-330, Hydran HW-340, and Hydran HW-350 (all manufactured by Dainippon Ink Chemical Co., Ltd.), Superflex 100, Superflex 130, and Superflex 150. Superflex 170 (all manufactured by Daiichi Kogyo Co., Ltd.), Adeka Bontighter HUX-206, Adeka Bontighter HUX-232, Adeka Bontighter HUX-360, Adeka Bontighter HUX-540 (all manufactured by ADEKA), and the like.

Examples of the epoxy resin include an epoxy compound obtained by a reaction of a polyphenol compound and epichlorohydrin, a cationic epoxy resin obtained by adding an amine to the epoxy compound, and a polybasic acid addition. An anionic epoxy resin obtained by introducing an acid group to the epoxy compound, and modifying the epoxy compound and/or the cationic or anionic epoxy resin with an acrylic acid modification or a urethane modification The obtained modified epoxy resin or the like.

The epoxy compound preferably has a number average molecular weight of from 400 to 4,000, particularly preferably from 800 to 2,000, an epoxy equivalent of from 190 to 2,000, and particularly preferably from 400 to 1,000. Examples of the polyphenol compound include bis(4-hydroxyphenyl)-2,2-propane, 4,4-dihydroxybenzophenone, and bis(4-hydroxyphenyl)-1,1-ethane. , bis(4-hydroxyphenyl)-1,1-isobutane, bis(4-hydroxy-tri-butylphenyl)-2,2-propane, bis(2-hydroxynaphthyl)methane, 1, 5-dihydroxynaphthalene, bis(2,4-dihydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)-1,1,2,2-ethane, 4,4-dihydroxydiphenylanthracene, Phenolic novolac resin, cresol novolak resin, and the like.

As the above acrylic resin, for example, (methyl) ) methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylate Acrylates such as glycerides, aminoethyl (meth)acrylates, homopolymers, copolymers of methacrylates, and monomers copolymerizable therewith such as styrene, acrylonitrile, acrylic acid, methacrylic acid, horse Copolymers of acid, acrylamide, N-methylol acrylamide, diallylamine, and the like. The acrylic resin may be an acrylic resin obtained by introducing an anionic group such as an acid group or a cationic group such as an amine group into the resin, neutralizing these groups, and dispersing or dissolving them in water. Further, it may be an aqueous emulsion obtained by emulsion polymerization using a surfactant or a reactive emulsifier, or a soap-free emulsion using a water-soluble polymer as an emulsifier.

As the above polyolefin resin, there is exemplified by using ammonia or an amine. A polyolefin resin obtained by dispersing a copolymer of ethylene and acrylic acid or methacrylic acid in water, and a polyolefin resin obtained by forcibly emulsifying a copolymer of ethylene and vinyl alcohol with a surfactant.

Hydrolyzed condensate (B)

The hydrolysis condensate of the component (B) as the metal surface treatment composition of the present invention is an epoxy group-containing decane coupling agent (a) and at least one alkoxydecane compound represented by the following formula [1] and/or The condensate (b) of the alkoxydecane compound (hereinafter, abbreviated as "alkoxydecane (condensate) (b)")), (R) _4-n- Si-( X) _n [1]

(wherein R represents a carbon which may be substituted by a substituent having no reactivity A hydrocarbon group having 1 to 18 atoms, X represents an alkoxy group, and n represents an integer of 1 to 3).

The epoxy group-containing decane coupling agent (a) is not particularly limited as long as it is a decane coupling agent having at least one epoxy group and a hydrolyzable group in one molecule. The hydrolyzable group is not particularly limited, and preferred examples thereof include an alkoxycarbenyl group directly bonded to a ruthenium element.

Specific examples of the epoxy group-containing decane coupling agent (a) include γ-glycidoxypropyltrimethoxydecane and γ-glycidoxypropylmethyldimethoxydecane. As the γ-glycidoxypropyltriethoxydecane, etc., γ-glycidoxypropyltrimethoxydecane and γ-glycidoxypropyltriethoxydecane can be preferably used.

The alkoxydecane compound represented by the formula [1] in the alkoxydecane (condensate) (b) may be a trialkoxydecane compound, a dialkoxydecane compound or a monoalkoxy group. The decane compound is preferably a trialkoxy decane compound from the viewpoint of solubility in an aqueous medium.

Examples of the trialkoxydecane compound include methyltrimethoxydecane, methyltriethoxydecane, methyltripropoxydecane, ethyltrimethoxydecane, and ethyltriethoxydecane. Propyltrimethoxydecane, propyltriethoxydecane, butyltrimethoxydecane, pentyltrimethoxydecane, hexyltrimethoxydecane,octyltrimethoxydecane,methyltris(methoxyB) Oxy) decane, ethyl tris(methoxyethoxy)decane, 3,3,3-trifluoropropyltrimethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, vinyl Tris(methoxyethoxy) And decane, phenyltrimethoxydecane, phenyltriethoxydecane, and the like. Among them, methyl trimethoxy decane, methyl triethoxy decane, methyl tripropoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, propyl trimethoxy group are particularly preferred. Decane, propyltriethoxydecane, butyltrimethoxydecane, methyltris(methoxyethoxy)decane, ethyltris(methoxyethoxy)decane.

As the above mono or dialkoxydecane compound, for example Examples thereof include monoalkoxy decane such as trimethyl methoxy decane, trimethyl ethoxy decane, trimethyl propoxy decane, triethyl methoxy decane, and triethyl ethoxy decane. Dimethoxy decane, dimethyl diethoxy decane, dimethyl dipropoxy decane, diethyl dimethoxy decane, diethyl diethoxy decane, methyl ethyl dimethoxy a dialkoxy decane such as decane, methyl ethyl diethoxy decane or dipropyl trimethoxy decane.

As the condensate of the alkoxydecane compound, a condensate having an average degree of polymerization of from 1.5 to 10, preferably from 1.5 to 5, can be used.

The hydrolysis condensate (B) can be preferably obtained by blending the above epoxy group-containing decane coupling agent (a) with the alkoxy decane (condensate) (b) in the former/the latter. It is obtained in the range of 3/1 to 1/3, more preferably 2/1 to 1/2, and a hydrolysis condensation reaction is carried out.

The hydrolytic condensation reaction is preferably carried out by using an epoxy group-containing decane coupling agent (a) and an alkoxy decane (condensate) (b) in an aqueous medium containing an acid catalyst as needed. For example, the reaction is carried out at 20 to 100 ° C for 0.5 to 20 hours, preferably at 40 to 90 ° C for about 1 to 10 hours. Epoxy-containing decane coupling agent (a) and alkoxy group in aqueous medium The total of both decane (condensate) (b) is in the range of 3 to 40% by mass, preferably in the range of 5 to 30% by mass. The weight average molecular weight of the hydrolysis condensate (B) is in the range of 400 to 20,000, preferably in the range of 500 to 12,000.

In the present specification, the weight average molecular weight of the hydrolysis-condensation product (B) is a value obtained by the retention time (retention capacity) of a standard polystyrene having a known molecular weight measured under the same conditions. The value obtained by converting the retention time (retention capacity) measured by gel permeation chromatography (GPC) into the molecular weight of polystyrene. "HLC-8120GPC" (trade name, manufactured by Tosoh Corporation) can be used as a gel permeation chromatograph device, and a "TSKgel GMHHR-L" (trade name, manufactured by Tosoh Corporation) is used as a column, and a differential refractometer is used. The detector can be measured under the conditions of a mobile phase: dimethylformamide (containing 0.5% by mass of triethanolamine), a measurement temperature of 25 ° C, and a flow rate of 1 mL/min.

The amount of the hydrolysis-condensation product (B) is in the range of 0.1 to 40 parts by mass, preferably 5 to 20 parts by mass, based on 100 parts by mass of the resin solid content of the aqueous organic resin (A).

Colloidal cerium oxide (C)

The colloidal cerium oxide as the component (C) of the metal surface treatment composition of the present invention is preferably a colloidal dioxide obtained by stabilizing ultrafine particles of cerium oxide (SiO ₂ ) by sodium or ammonium. Hey. The ultrafine particles of cerium oxide (SiO ₂ ) are preferably spherical cerium oxide which can be polymerized by a siloxane chain and which has a hydroxyl group on the surface thereof. Further, the size of the fine particles is preferably in the range of 1 to 50 nm, and particularly preferably in the range of 5 to 20 nm.

Colloidal cerium oxide which can be used as the component (C) can be For the acquisition of commercially available products, for example, Snowtex N, Snowtex S, Snowtex NXS, Snowtex C (both manufactured by Nissan Chemical Industries Co., Ltd., trade name), Adelite AT-20A, Adelite AT-2045 (Adeka Co., Ltd.) System, trade name) and so on.

Further, the colloidal cerium oxide (C) may be a colloidal cerium oxide obtained by treating the above-mentioned colloidal cerium oxide with a decane coupling agent, and in the case of treatment with a decane coupling agent, it may be relative to a colloidal state. The solid content of the cerium oxide is 100 parts by mass, and 1 to 50 parts by mass of the decane coupling agent is added, preferably 3 to 30 parts by mass, more preferably 5 to 20 parts by mass, and the reaction is carried out.

As the above decane coupling agent, for example, vinyl three Methoxy decane, vinyl triethoxy decane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-epoxy Propoxypropyltriethoxydecane, γ-aminopropyltrimethoxydecane, N-β(aminoethyl)γ-aminopropyltrimethoxydecane, γ-methylpropenyloxy Propyltrimethoxydecane, and the like.

By incorporating colloidal cerium oxide in the composition of the present invention (C), whereby the adhesion of the obtained treatment film to the substrate can be improved, and the corrosion resistance of the film can be improved, but when it is excessively blended, the processability of the film is lowered, the adhesion is deteriorated, and the surface is damaged. The barrier property of the treatment film is not able to suppress the permeation of corrosion factors in a corrosive environment, and it is easy to reduce the corrosion resistance.

The amount of colloidal cerium oxide (C) blended based on the aforementioned water-based 100 parts by mass of the resin solid content of the resin dispersion (A), which is 5.0 to 50 The parts by mass are preferably in the range of 10 to 30 parts by mass, which is suitable from the above viewpoints.

Water metal surface treatment agent

The aqueous metal surface treatment agent of the present invention contains the above-mentioned aqueous organic resin (A), hydrolysis condensate (B), and colloidal cerium oxide as essential components, and may further contain an organic phosphate compound (D) as needed. Rust metal compound (E), wax (F), and the like. In the aqueous metal surface treatment agent of the present invention, it is preferred that the above components are stably dissolved or dispersed in water. The above components (D) to (F) will be described below.

Organic phosphate compound (D)

In the aqueous metal surface treatment agent of the present invention, the organic phosphate compound (D) may be contained as needed for the purpose of improving the adhesion of the surface treatment film to the metal surface. The organic phosphoric acid compound (D) can further improve the rust prevention property together with the colloidal cerium oxide, and can also contribute to the improvement of the storage stability of the metal surface treatment agent.

As the organic phosphoric acid compound (D), preferred are, for example, 1-hydroxymethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxypropane-1, a hydroxyl group-containing organic phosphorous acid such as 1-diphosphonic acid, a carboxyl group-containing organic phosphorous acid such as 2-hydroxyphosphoninoacetic acid or 2-phosphonium butane-1,2,4-tricarboxylic acid, and a salt thereof Wait. Among them, 1-hydroxyethane-1,1-diphosphonic acid is particularly preferred.

In the case where the organic phosphate compound (D) is blended in the aqueous metal surface treatment agent of the present invention, the amount thereof is 0.1 to 5.0 by mass based on 100 parts by mass of the resin solid content of the aqueous organic resin (A). The range of parts is preferably in the range of 0.5 to 3.0 parts by mass.

Rust-proof metal compound (E)

In the aqueous metal surface treatment agent of the present invention, the rust preventive metal compound (E) may be contained as needed for the purpose of improving the rust prevention property of the surface treatment film.

Examples of the rust preventive metal compound (E) include metal compounds having a metal element such as titanium, zirconium, hafnium, vanadium, magnesium, manganese, zinc, tungsten, molybdenum, aluminum, nickel, cobalt, or calcium.

Examples of the rust preventive metal compound (E) include the above-mentioned metal elements and inorganic acids such as hydrofluoric acid, phosphoric acid, carbonic acid, nitric acid, and sulfuric acid, or formic acid, acetic acid, butyric acid, oxalic acid, succinic acid, lactic acid, and L- a salt of an organic acid such as ascorbic acid, tartaric acid, citric acid, DL-malic acid, malonic acid, maleic acid, phthalic acid; an oxide of these metal elements; an alkoxide of the metal, an alkylpyruvate, an alkane a complex salt such as a dioleate, a lactate, an ammonium salt or a stearate. These metal compounds may be anhydrate or a hydrate.

Typical examples of the metal compound (E) include: basic zirconium carbonate (ZrCO ₄ .ZrO ₂ .8H ₂ O), ammonium zirconium carbonate, nickel sulfate, zirconium nitrate, vanadyl sulfate, zirconium sulfate, aluminum nitrate, Nickel acetate, zirconium acetate, vanadium oxide, ammonium metavanadate, vanadium pentoxide (V ₂ O ₅ ), phosphorus vanadium molybdate, hexafluorotitanate (H ₂ TiF ₆ ), hexafluorozirconic acid (H ₂ ZrF ₆ ) And hydrofluoric acid such as hexafluoroantimonic acid (H ₂ HfF ₆ ) or hexafluoroaluminate (H3AlF ₆ ), and salts of these hydrofluoric acids (for example, sodium salt, potassium salt, lithium salt, ammonium salt, amine salt, zinc salt, etc.) )Wait. Among the above metal compounds, a metal compound of vanadium or zirconium is particularly preferable. As the rust preventive metal compound (E), the metal compounds may be used singly or in combination of two or more.

It is considered that the rust preventive metal compound (E) has the following effects : Improving the film density by generating ions in water, controlling the corrosion potential of the metal surface in a corrosive environment, controlling the redox reaction, forming a film on the metal surface by using a thin film film, and crosslinking with a functional group in a film component. , thereby improving corrosion resistance.

Blending rust prevention in the aqueous metal surface treatment agent of the present invention In the case of the metal compound (E), the amount of the metal compound (E) is from 0.1 to 30 parts by mass, preferably from 1.0 to 20 parts by mass, based on 100 parts by mass of the resin solid content of the aqueous organic resin (A). range.

Wax (F)

In the aqueous metal surface treatment agent of the present invention, the wax (F) may be contained as needed for the purpose of improving the lubricity of the surface treatment film.

The wax (F) is not particularly limited as long as it can improve the lubricity of the surface-treated film, and examples thereof include paraffin wax, microcrystalline wax, petroleum wax such as polyethylene and polypropylene, and fluorine-containing organic compound. They are used alone or in combination. Examples of the fluorine-containing organic compound include a polymer obtained by substituting a hydrogen atom of a repeating unit of (PE ₂ -CH ₂ )-polyethylene (PE) with a fluorine atom, that is, polyvinyl fluoride (PVF), poly Various polymer fluorine-containing organic compounds such as vinylidene fluoride (PVdF), polytrifluoroethylene (PTrFE), polytetrafluoroethylene (PTFE), and copolymers of these polymers and olefins or modified products thereof.

The wax (F) is preferably a wax having a softening point of 50 to 160 ° C as defined in JIS K 2351 from the viewpoint of improving lubricity. In addition, the particle size of the wax is small (1 μm or less), and the particle size is excellent in the stability of the surface treatment agent, but it is large in terms of improvement in lubricity ( Since the particle diameter is several μm to 10 μm, it is preferable to appropriately select one or two or more kinds depending on the purpose of use.

As the kind of the wax (F), a polyethylene wax or a polypropylene wax can be preferably used.

When the wax (F) is blended in the aqueous metal surface treatment agent of the present invention, the amount thereof is 0.5 to 50 parts by mass based on 100 parts by mass of the resin solid content of the aqueous organic resin (A). It is preferably in the range of 1.0 to 20 parts by mass.

The aqueous metal surface treatment agent of the present invention contains both a bath-forming composition (concentrated liquid) and a working composition (diluted liquid). The concentration of all the solid components in the composition for building a bath is preferably from 10 to 40% by mass, more preferably from 15 to 30% by mass. The concentration of all solid components in the working composition is preferably from 1 to 40% by mass, more preferably from 5 to 30% by mass.

The surface treatment agent of the present invention has a viscosity of 2.5 mPa measured at a measurement temperature of 20 ° C and a B-type rotational viscometer of 60 rpm. In the following, this is preferable from the viewpoint of the coatability of the surface treatment agent.

In addition to the above-mentioned components, the water-based metal surface treatment agent of the present invention may further contain a pH adjuster (acid or alkali), a filler, a colorant, a surfactant, an antifoaming agent, a leveling agent, and the like, as needed. Antibacterial agents, etc.

The pH in the case of using the aqueous metal surface treatment agent of the present invention as the working composition is preferably in the range of 5.0 to 10.0, more preferably in the range of 6.0 to 9.0. In this case, when the pH of the surface treatment composition is increased as a pH adjuster, ammonia water, an amine compound, or the like can be used. An alkali metal hydroxide such as sodium hydroxide or an alkali metal carbonate such as sodium carbonate or the like is preferably an organic carboxylic acid such as formic acid, acetic acid, propionic acid or lactic acid, or an aminotrimethylene phosphonic acid, when the pH is lowered. An acid component such as an organic phosphonic acid such as 1-hydroxyethane-1,1-diphosphonic acid is adjusted.

Examples of the filler include fine powders such as cerium oxide, talc, cerium oxide, calcium carbonate, and mica, and examples of the filler used as the extender pigment. Examples of the colorant include a coloring pigment, a dye, and the like.

Metal surface treatment method

The metal surface treatment method of the present invention is characterized in that the above-described aqueous metal surface treatment composition of the present invention is applied to a metal coated article and dried, and is made of a metal using the aqueous metal surface treatment composition of the present invention. A method of treating a film on the surface of the object to be coated.

In the present invention, the "treatment film" includes not only a continuous treatment film but also a discontinuous treatment product because the treatment adhesion amount is small and the continuous treatment film cannot be formed.

The above-mentioned metal coated material, if it is a metal raw material, does not Any limitation is exemplified by iron, copper, aluminum, tin, zinc, an alloy containing these metals, and a plated steel sheet or a vapor-deposited product obtained based on these metals. Among them, a metal plate can be preferably used.

Examples of the metal plate used as the object to be coated include cold-rolled steel sheets, hot-dip galvanized steel sheets, electrogalvanized steel sheets, galvanized alloys (alloys such as zinc-iron, zinc-aluminum, and zinc-nickel) and aluminum-plated steel sheets. , stainless steel plate, copper plated steel plate, tin plated steel plate, aluminum plate, copper plate, etc. Among them, a galvanized steel sheet (including any one of a hot-dip galvanized steel sheet and an electrogalvanized steel sheet) and a galvannealed steel sheet can be preferably used.

Coating the aqueous gold of the present invention on the above-mentioned metal coated article Before the surface treatment composition, the metal coating may be surface-adjusted by one or more of degreasing, pickling, hot water washing, lotion washing, etc., in either case, preferably at the end. Washed. Further, the liquid temperature of the aqueous metal surface treatment composition of the present invention at the time of application may be normal temperature, but may be cooled or warmed as desired.

On the above-mentioned metal coated object, by roll coating, spraying The aqueous metal surface treatment composition of the present invention is applied by a known method such as a coating method, a brush coating method, an electrostatic coating method, a immersion method, an electrodeposition coating method, a curtain coating method, or a roll coating method, and is dried to form a treatment film. Further, the surface treatment film described above may be formed only on one surface of the metal coated object or may be formed on both surfaces.

The amount of the coating film to be obtained by the aqueous metal surface treatment composition of the present invention is not particularly limited, but is generally 0.4 to 4.0 g/m ² , preferably 0.7 to 3.0 g from the viewpoint of corrosion resistance and workability. The range of /m ² .

The drying conditions of the treatment film may be appropriately set. However, when the coating material obtained by applying the coil coating method or the like is continuously baked, the maximum temperature of the raw material is usually 80 to 200 ° C, preferably 90 °. Drying was carried out by heating at 120 ° C for 5 to 60 seconds. In the case of batch baking, for example, it can also be dried by heating at an ambient temperature of 100 to 180 ° C for 1 to 30 minutes.

Surface treated metal sheet

The surface treated metal sheet of the present invention is: using the aqueous gold of the present invention A surface-treated metal sheet obtained by surface-treating a surface of a metal coated object. The metal coated article of the surface-treated metal sheet of the present invention has a plate-like shape, and the surface-treated metal sheet can be obtained by the above-described metal surface treatment method of the present invention.

In the surface-treated metal sheet of the present invention, the amount of the coating film obtained by the aqueous metal surface treatment composition of the present invention is in the range of 0.4 to 4.0 g/m ² from the viewpoint of corrosion resistance and workability, and is preferably A range of 0.7 to 3.0 g/m ² .

In the treatment film of the surface-treated metal sheet of the present invention, an upper layer film such as a colored coating film or a transparent coating film may be further formed for the purpose of improving the appearance, durability, and other functions. The formation of the upper layer film may be carried out before the surface-treated metal sheet of the present invention is subjected to a molding process, but it is preferably carried out after the molding process.

Hereinafter, the present invention will be more specifically described by exemplifying production examples, examples, and comparative examples. However, the invention is not limited thereto.

[Examples]

The present invention will be specifically described by way of examples and comparative examples, and the present invention is not limited to these examples. In each example, "parts" and "%" are based on quality standards unless otherwise specified. The amount of film on the film is based on the amount of dry film.

Production of hydrolysis condensate (B)

Manufacturing example 1

Into a four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 1000 parts of deionized water, 1000 parts of methanol, and 10 parts of acetic acid were blended, and the temperature was raised and maintained at 40 °C. It takes 1 hour to be used as an epoxy group-containing decane coupling agent. A mixture of 101 parts of 3-glycidoxypropyltrimethoxydecane (a) and 58 parts of methyltrimethoxydecane as the alkoxydecane compound (b) was added dropwise to the above flask. After completion of the dropwise addition, the mixture was further stirred for 1 hour, and then distilled under reduced pressure at 60 ° C to distill off the blended methanol and methanol formed by hydrolysis. While the deionized water was appropriately added so that the solid content concentration was kept at 10% or less, the vacuum distillation was continued until the methanol concentration measured by gas chromatography reached 1% or less. The hydrolyzed condensate liquid was produced by adjusting so that the final solid content became 10%. In the production of the hydrolysis-condensation product, the ratio of the elemental ratio of (a)/(b) using the raw material is 1/1.

Manufacturing example 2~6

The hydrolysis condensate of Production Examples 2 to 6 was produced in the same manner as in Production Example 1 except that the types and amounts of the components (a) and (b) were set as shown in Table 1 below.

Manufacturing Example 7

Into a four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 58 parts of methyltrimethoxydecane, 10 parts of methanol, 1 part of acetic acid, and 7 parts of water were placed, and the mixture was stirred at 40 ° C for 1 hour under reduced pressure. Distillation was carried out until no volatiles were obtained, thereby obtaining a methyltrimethoxydecane oligomer which was a component (b). 101 parts of 3-glycidoxypropyltrimethoxydecane as the component (a) was added thereto to prepare a decane mixture.

To another with a mixer, reflux condenser, thermometer In a four-necked flask, 1000 parts of deionized water, 1000 parts of methanol, and 9 parts of acetic acid were blended, and the temperature was raised and kept at 40 °C. The decane mixed droplets prepared above were added to the flask over 1 hour. Stir for 1 hour and then at 60 ° C The vacuum distillation was carried out, and the blended methanol and methanol formed by hydrolysis were distilled off. While the deionized water was appropriately added in such a manner that the solid content concentration was maintained at 10% or less, the distillation under reduced pressure was continued until the methanol concentration measured by gas chromatography reached 1% or less. The hydrolyzed condensate liquid of Production Example 7 was produced by adjusting so that the final solid content became 10%. In the production of the hydrolysis-condensation product, the ratio of the elemental ratio of (a)/(b) using the raw material is 1/1.

The hydrolysis condensate produced by the above Production Examples 1 to 7 The weight average molecular weight obtained by GPC measurement is in the range of 500 to 12,000.

Manufacture of metal surface treatment compositions

Examples 1 to 21 and Comparative Examples 1 to 8

The mixture was blended according to the blending ratio shown in Table 2 below, and deionized water was added thereto so as to have a solid content concentration of 25% by mass, and the mixture was sufficiently stirred to obtain each metal surface-treating composition. In addition, the formulation of Table 2 is expressed in terms of solid component quality.

Regarding the storage stability of each surface treatment composition obtained The properties were evaluated according to the test methods described below. The test results obtained are shown in Table 2 below.

Storage stability: 500 g of each surface treatment agent was placed in a glass container having a content of 1 L, sealed, and stored in a thermostatic chamber at 40 ° C for 14 days. Thereafter, the temperature was returned to room temperature, and the state in the container was visually observed, and evaluated according to the following criteria:

◎: No significant thickening, soft agglomeration and/or separation was found, which was good.

○: Soft agglomeration and/or separation were confirmed, but it was uniform by stirring for 10 minutes or less.

△: It was confirmed that there was soft agglomeration and/or separation, and it became uniform by stirring for more than 10 minutes and less than 60 minutes.

×: It was confirmed that there was hard agglomeration and/or separation, and it was not uniform even after stirring for more than 60 minutes.

The types of the organic resin (A) in Table 2 are as follows.

A1: Adeka Bontighter HUX-206 (made by ADEKA), trade name, polyurethane resin aqueous dispersion, pH 8, solid content 30%, A2: Adeka Bontighter HUX-540 (made by ADEKA Co., Ltd., trade name, anionic polyurethane resin aqueous dispersion, pH 8, resin acid value: 32 mgKOH/g, solid content: 30% by mass), A3: Watersol CD- 550LAP (DIC system, trade name, epoxy resin aqueous solution, pH 9, solid concentration 40%), A4: Modepics 302 (Arakawa Chemical Industry Co., Ltd., trade name, epoxy resin aqueous solution, pH 8. 5, solid content concentration 33%), A5: Aquabrid CC234 (DIC (stock), trade name, acrylic resin aqueous liquid, pH 7, solid concentration of 34%), A6: Chemipearl S-100 (Mitsui Chemical Co., Ltd.) The product name, sodium-salt dispersion of ethylene-acrylic acid copolymer, ion-crosslinked polymer, pH 10, solid content concentration: 27%).

The types of the colloidal cerium oxide (C), the organic phosphoric acid compound (D), the rust preventive metal compound (E), and the wax (F) in Table 2 are as follows.

C1: Snowtex NSX (Nissan Chemical Industry Co., Ltd., colloidal cerium oxide aqueous dispersion, pH 9.0~10.0, particle size 5nm), C2: Snowtex N (Nissan Chemical Industry Co., Ltd., colloidal dioxide Hydrophobic dispersion, pH 9.0~10.0, particle size 10~20nm), D1:1-hydroxyethane-1,1-diphosphonic acid, E1: ammonium metavanadate, E2: ammonium zirconium carbonate, E3: six Ammonium zirconium fluoride, F1: LUVAX1151 (manufactured by Nippon Steel Co., Ltd., polyethylene wax, ring and ball softening point 107 ° C).

X and Y described in the column of the hydrolysis condensate (B) in Table 2 However, it is not a hydrolysis condensate, but it is described in the column for convenience, and has the following meaning.

X: γ-glycidoxypropyltrimethoxydecane, Y: methyltrimethoxydecane.

Examples 22 to 48 and Comparative Examples 9 to 16

Using the above respective surface treatment compositions, surface-treated metal sheets were obtained in the manner shown in Table 3 below. The types of metal sheets in Table 3 are as follows.

(metal plate type)

EG: double-sided electrogalvanized steel sheet with a plating adhesion of 20 g/m ^{2 on} one side and 0.8 mm thickness, GA: two-sided alloyed Zn-Fe melting with a plating amount of 45 g/m ^{2 on} one side and 0.8 mm thickness Plated steel sheet, GI: A double-sided hot-dip galvanized steel sheet having a plating adhesion amount of 60 g/m ^{2 on} one side and 0.6 mm in thickness.

(processing steps)

In each of the examples, an aqueous dispersion of "CC-561B" (manufactured by Cee-Bee Chemical Co., Ltd., Japan No. 3 equivalent) aqueous dispersion (2%) was used for the metal plate (EG) at a liquid temperature of 65 ° C. The degreasing was carried out for 60 seconds, followed by hot water washing at a liquid temperature of 50 ° C and an injection time of 20 seconds. With respect to the obtained alkali degreased metal sheet, the surface treatment composition obtained in each of the above examples was applied by a bar coater in accordance with the combination shown in Table 3 below and the dry film quality, and the temperature reached 110 ° C according to the highest temperature of the metal plate. The method was heat-dried for 15 seconds to obtain each surface-treated metal sheet.

The surface-treated metal sheets of the respective examples obtained were evaluated for the film properties by the following test methods, and the results obtained are shown in Table 3 below.

Appearance after production; the appearance of the surface treated metal sheet obtained was evaluated below.

◎: No abnormalities

○: 1 to 5 or less spots having a length of 0.1 to 5 mm are produced in a square of 30 cm × 30 cm.

△: 5 to 19 spots having a long diameter of 0.1 to 5 mm are produced in a square of 30 cm × 30 cm.

×: 20 or more spots having a long diameter of 0.1 to 5 mm were produced in a square of 30 cm × 30 cm.

Corrosion resistance: A test plate in which the end surface portion and the back surface portion of the surface-treated metal sheet were sealed was subjected to a salt spray test prescribed in JIS Z 2371 until 360 hours, and the degree of rust of the treated film surface was evaluated according to the following criteria.

◎: No occurrence of white rust was observed.

○: The occurrence of white rust was confirmed, but the degree of occurrence was less than 5% of the area of the treated film.

△: The degree of generation of white rust is 5% or more and less than 20% of the area of the treated film.

×: The degree of generation of white rust is 20% or more of the area of the treated film.

Fingerprint resistance: Vaseline was applied to one-half of the coated surface of the test plate and placed in a thermostatic chamber at 20 ° C for 24 hours, then the Vaseline was wiped off with gauze, and the coated surface after the removal of Vaseline and the uncoated Vaseline were measured. The color difference of the coated surface was evaluated according to the following criteria. Further, the color difference measurement was performed by using a color difference meter "CR-100" manufactured by Minolta.

○: The color difference (ΔE) is less than 2

×: The color difference (ΔE) is 2 or more.

Deep drawing processability: For the surface-treated metal sheet, a deep drawing test was carried out at 20 ° C using a metal sheet deep drawing tester type 142 manufactured by Erichsen. The conditions of the processing test were a sheet support pressure of 1500 kg, a punch diameter of 50 mm, a prototype mold diameter of 110 mm, a draw ratio of 2.2, and a drawing speed of 10 mm/sec, and were evaluated according to the surface condition of the workpiece according to the following evaluation criteria.

◎: There was no deposit on the mold, and no scratch was found on the surface of the workpiece.

○: A small amount of deposits were present on the mold, and minute scratches were confirmed on the surface of the workpiece.

△: There was a slight amount of deposit on the mold, and although the surface of the workpiece was not on the entire surface, it was confirmed that there were many scratches.

X: A large amount of deposits were present on the mold, and significant scratches were observed on the entire surface of the workpiece, or processing was impossible.

Adhesiveness of the upper coating film: "Magicron 1000 White" (acrylic resin-melamine resin coating, white) manufactured by Kansai Paint Co., Ltd. at a temperature of 150 ° C was applied to the surface of the surface-treated metal sheet so as to have a dry film thickness of 25 μm. The test panels were obtained by baking for 20 minutes. The test plate was immersed in boiling water at about 98 ° C for 2 hours, then lifted up and left at room temperature for 2 hours. On the coated surface of the test coated plate, 11 vertical and horizontal sections of the base of the checkerboard lattice were engraved by a knife. Scars made There are 100 squares of 1mm square. The celluloid adhesive tape is adhered to the checkerboard portion of the checkerboard, and the tape is peeled off in an instant. The number of the checkerboard coating films peeled off from the test coated sheets at the time of peeling off the tape was evaluated according to the following criteria.

◎: No peeling of the upper coating film was observed.

○: It was confirmed that there were 1 to 20 checkerboard peeling films, but it was within the practical range.

△: It was confirmed that there were peeling of 20 to 50 checkerboard coating films.

×: It was confirmed that there were peeling of five or more checkerboard coating films.

Claims (8)

An aqueous metal surface treatment agent comprising: (A) at least one water-based organic selected from the group consisting of polyurethane resin, epoxy resin, acrylic resin, and polyolefin resin, in terms of solid content 100 parts by mass of the resin; and 100 parts by mass of the resin solid content of the aqueous organic resin (A), the (B) epoxy group-containing decane coupling agent (a) and the following formula [1] are contained according to the solid content. At least one alkoxydecane compound and/or a hydrolysis condensate of the condensate (b) of the alkoxydecane compound (0.1 to 40 parts by mass), and (C) colloidal ceria 5.0 to 50 parts by mass, (R) _4-n -Si-(X) _n [1] (wherein R represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted by a substituent having no reactivity, X represents an alkoxy group, and n represents 1 to 3 Integer). The aqueous metal surface treating agent of claim 1, wherein the epoxy group-containing decane coupling agent in the component (B) is from γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyl At least one compound selected from the group consisting of methyl dimethoxy decane and γ-glycidoxy propyl triethoxy decane, and the alkoxy decane compound in the component (B) is derived from methyl trimethoxy decane. Methyl triethoxy decane, methyl tripropoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, propyl trimethoxy decane, propyl triethoxy decane, butyl trimethoxy Base decane, pentyltrimethoxydecane, hexyltrimethoxydecane, octyltrimethoxydecane, methyltris(methoxyethoxy)decane, ethyltris(methoxyethoxy)decane, 3 , 3,3-trifluoropropyltrimethoxydecane, vinyltrimethoxyanthracene At least one trialkoxydecane selected from the group consisting of an alkane, a vinyltriethoxydecane, a vinyltri(methoxyethoxy)decane, a phenyltrimethoxydecane, and a phenyltriethoxydecane. The aqueous metal surface treating agent according to claim 1 or 2, wherein the epoxy group-containing decane coupling agent (a) in the component (B) and the alkoxydecane compound and/or the alkoxydecane compound are condensed The blending ratio of (b) is in the range of 3/1 to 1/3 according to the ratio of the former/the latter. The aqueous metal surface treatment agent according to claim 1 or 2, wherein the (D) organic phosphate compound is further contained in an amount of 0.1 to 5.0 parts by mass based on the solid content based on 100 parts by mass of the resin solid content of the aqueous organic resin (A). The water-based metal surface treatment agent according to claim 1 or 2, wherein the (E) rust-preventing metal compound is further contained in an amount of 0.1 to 30 parts by mass based on the solid content based on 100 parts by mass of the resin solid content of the aqueous organic resin (A). The aqueous metal surface treatment agent according to claim 1 or 2, wherein the solid content of the resin is 100 to 50 parts by mass based on the solid content of the resin solid content of the aqueous organic resin (A). A metal surface treatment method according to any one of claims 1 to 6, wherein the aqueous metal surface treatment composition is applied to a metal coating material and dried. A surface-treated metal sheet obtained by surface-treating a surface of a metal coated object by using the aqueous metal surface treatment composition according to any one of claims 1 to 6.